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Measuring the concentration of PAHs in the freely dissolved phase is crucial for assessing ecological impacts in the marine environment. However, various environmental conditions make short-term monitoring challenging. This study used an optimized High Speed Rotation-Type Passive Sampling Device (HSR-PSD) equipped with linear low-density polyethylene (LLDPE) to conduct the first nationwide monitoring of freely dissolved PAHs in Korean coastal waters. The HSR-PSD enabled faster short-term monitoring by measuring C free of PAHs within 12 h and was less affected by environmental conditions compared to conventional PSDs. Σ 15 PAH concentrations ranged from 2.8 to 9.4 ng/L, with significantly higher levels on the western coast. Anthropogenic activities and oceanic conditions affected C free distribution in coastal areas. Based on C free , the estimated PAH levels in bivalves and fish were aligned with reported tissue concentrations, exhibiting low ecological risk to aquatic organisms. Therefore, the HSR-PSD with LLDPE is a suitable tool for nationwide short-term monitoring. • The freely dissolved PAHs were first monitored nationwide in Korean coastal waters. • Automatic passive sampler with LLDPE is an suitable tool for short-term monitoring. • Anthropogenic activities and oceanic conditions together affect C free distribution. • Estimated PAHs level in bivalves and fish using C free align with tissue concentration. [ABSTRACT FROM AUTHOR]

Organophosphate esters (OPEs) are emerging contaminants that serve as alternatives to regulated substances in aquatic environments. A nationwide large-scale assessment for OPEs, including point sources, remains insufficient. To address this issue, we aimed to investigate OPEs occurrence and novel OPEs via comprehensive target, suspect and non-target analysis. Among the 11 target OPEs, 10 were detected at sampling sites distributed evenly nationwide. The highest mean concentrations were measured for tris-(2-butoxyethyl) phosphate (TBOEP) and tris(2-chloroisopropyl) phosphate (TCIPP). The multivariate statistical analysis revealed that TBOEP and TCIPP are essential components for assessing total OPEs pollution. The systematic risk assessment results evaluated the overall risk contribution of TBOEP and the significant risk impact of 2-ethylhexyl diphenyl phosphate. Promising suspect and non-target analysis enabled frequent detection and identification of 6 antioxidant transformation products (TPs), as well as the tentative identification of 14 OPEs and TPs, including 3 di-OPEs. Based on sampling site classification, we confirmed that major OPEs are significantly discharged near point sources. We believe that this is the first attempt to assess the nationwide risk and potential sources of OPEs in Korean surface waters, providing insights that could support further prioritization and regulation efforts. [Display omitted] • Nationwide monitoring showed OPEs, especially TBOEP, as predominant in Korean surface waters. • Multivariate analysis identified TBOEP and TCIPP as essential components for OPEs assessment. • TBOEP had overall risk contribution, with EHDPP showing significant risk impact. • Suspect and non-target analysis identified 20 novel OPEs and antioxidant TPs. [ABSTRACT FROM AUTHOR]

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